Electronic and adsorption properties of halogen molecule X2 (X=F, Cl) adsorbed arsenene: First-principles study

The geometry, electronic structure, and adsorption properties of halogen molecule X₂(X = F, Cl) on arsenene were investigated using first-principles calculations. The adsorption of molecules was considered at various sites and in various orientations on the pristine arsenene (p-As) surface. Both molecules show chemisorption and the crystal orbital Hamiltonian population (COHP) analysis reveals the formation of strong X-As bonds. In particular, the adsorbed molecules spontaneously dissociate into atomic halogen atoms, with a diffusion barrier of 1.91 (1.72) eV for F₂(Cl₂). The adsorbed X₂ molecules induced distortions in the local geometry due to strong interaction with arsenene. Importantly, the formation of X-As bonding remarkably changed the electronic properties, evidenced by the decrease of the actual band gap due to the emergence of defect states within the band gap. For instance, the F₂ adsorbed arsenene system (F₂-As) exhibited an average band gap of 1.17 eV, and Cl₂ adsorbed arsenene (Cl₂-As) showed an average band gap of 0.83 eV. In particular, indirect to direct band gap transition was observed for some adsorption configurations. The reduction in band gap resulted in the enhancement of electrical conductivity. These findings suggest that the electronic properties of arsenene can be tuned by halogen decoration.